CN105268457A - Catalyst for cracking 1, 2-dichloroethane and method for catalyzing 1, 2-dichloroethane cracking - Google Patents
Catalyst for cracking 1, 2-dichloroethane and method for catalyzing 1, 2-dichloroethane cracking Download PDFInfo
- Publication number
- CN105268457A CN105268457A CN201510688115.9A CN201510688115A CN105268457A CN 105268457 A CN105268457 A CN 105268457A CN 201510688115 A CN201510688115 A CN 201510688115A CN 105268457 A CN105268457 A CN 105268457A
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- China
- Prior art keywords
- dichloroethanes
- chloride
- cracking
- cracking catalyst
- catalyst
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Links
- 238000005336 cracking Methods 0.000 title claims abstract description 62
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 18
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 11
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000001110 calcium chloride Substances 0.000 claims abstract description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- GZETWZZNDACBTQ-UHFFFAOYSA-N [Cl].C=C Chemical compound [Cl].C=C GZETWZZNDACBTQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for cracking 1, 2-dichloroethane, which comprises a carrier and a first metal chloride loaded on the carrier, wherein the first metal chloride is selected from calcium chloride, cesium chloride or a combination thereof. The invention also provides a method for catalyzing the cracking of 1, 2-dichloroethane, which comprises the step of carrying out cracking reaction on the 1, 2-dichloroethane gas in contact with a catalyst for cracking 1, 2-dichloroethane to generate vinyl chloride and hydrogen chloride. The catalyst can be used for cracking reaction under mild operation conditions, and the method has high conversion rate and high selectivity, and can reduce the production cost of vinyl chloride.
Description
Technical field
The invention relates to a kind of cracking catalyst, refer to a kind of 1,2-dichloroethanes cracking catalyst especially and with the method for its catalysis 1,2-dichloroethanes cracking.
Background technology
In petrochemical industry, manufacture VCM (vinylchoridemonomer, VCM) mode is by by 1,2-dichloroethanes (1,2-dichloroethane, ethylenedichloride, EDC) at high temperature carry out following heat scission reaction (thermalpyrolysis) and obtain:
Such as Ind.Eng.Chem.Res.2009,48,2801-2809 discloses and uses pyrolysis furnace (furnace) to carry out above-mentioned heat scission reaction, but, its reaction is temperature required up to 480-520 DEG C, but the energy resource consumption needed for high temperature is large, and can increase by-product concentration and carbon deposition quantity, therefore improves production cost.In addition, the EDC conversion ratio that above-mentioned heat scission reaction has is generally about less than 60%, and VCM is selective general about less than 98%.
Summary of the invention
Therefore, object of the present invention, is namely to provide a kind of 1,2-dichloroethanes cracking catalyst, can effectively overcomes aforementioned existing issue.
The invention provides a kind of 1,2-dichloroethanes cracking catalyst, comprise a carrier and be carried on the first metal chloride on described carrier, wherein, described first metal chloride is selected from calcium chloride, cesium chloride or its combination.
Therefore, another object of the present invention, is namely to provide a kind of catalysis 1, the method of 2-dichloroethanes cracking, comprises and makes 1,2-dichloroethanes gas with one as above 1, cracking reaction is carried out, to generate vinyl chloride and hydrogen chloride under 2-dichloroethanes cracking catalyst exposure.
Effect of the present invention is to utilize this 1,2-dichloroethanes cracking catalyst and the method passing through this catalysis 1,2-dichloroethanes cracking, can produce vinyl chloride, and have high conversion and high selectivity concurrently under relatively mild operating condition.
Below will be described in detail with regard to content of the present invention:
Preferably, the present invention 1,2-dichloroethanes cracking catalyst also comprises the second metal chloride be carried on described carrier, and wherein, this second metal chloride is selected from barium chloride, potassium chloride or its combination.
Preferably, be 100wt% meter with the gross weight of this 1,2-dichloroethanes cracking catalyst, the weight range of described first metal chloride is 9-80wt%.
Preferably, be 100wt% meter with the gross weight of this 1,2-dichloroethanes cracking catalyst, the weight summation scope of described first metal chloride and described second metal chloride is 9-80wt%.
Preferably, described carrier is selected from carbon material, inorganic oxide or its combination.More preferably, described carrier is in pelletized form or powdery.In a particular embodiment of the present invention, described carrier is active carbon.
Preferably, the surface area of described carrier is 100-1000m
2/ g.In a particular embodiment of the present invention, the surface area of described carrier is 900m
2/ g.
Preferably, the average particle size range of described carrier is 0.05-10mm.In a particular embodiment of the present invention, the average grain diameter of described carrier is 3mm.
Preferably, the method for the first metal chloride described in load and described second metal chloride is selected from excess solution impregnation method, incipient wetness (incipientwetnessimpregnation), ion-exchange, coprecipitation, vapour deposition process (vapordeposition) or its combination on the carrier.
Preferably, described 1,2-dichloroethanes cracking catalyst is filled in a fixed bed or a thermopnore.
Preferably, the temperature range of described cracking reaction is 150-300 DEG C.More preferably, the temperature range of this cracking reaction is 250-300 DEG C.In a particular embodiment of the present invention, the temperature of this cracking reaction is 250 DEG C.
Preferably, the holdup time scope of described 1,2-dichloroethanes gas on described 1,2-dichloroethanes cracking catalyst is 5-50 second.In a particular embodiment of the present invention, the holdup time of described 1,2-dichloroethanes gas on described 1,2-dichloroethanes cracking catalyst is 10 seconds.
Preferably, in described cracking reaction, gas space velocity (gashourlyspacevelocity, GHSV) scope hourly is 100-1000h
-1.In a particular embodiment of the present invention, gas space velocity hourly is 550-560h
-1.
Detailed description of the invention
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
Embodiment 1 load calcium chloride
1,2-dichloroethanes cracking catalyst of embodiment 1 obtains via following steps preparation:
A () (surface area is 900m by activated carbon
2/ g, average grain diameter is 3mm) prior to 90 DEG C at carry out surface treatment with 10wt% aqueous hydrochloric acid at reflux, then with pure water cleaning, and dry in vacuum drying oven.
B () in the dry state, above-mentioned for the 100g surface-treated activated carbon that completes is soaked in 10wt% calcium chloride water, add a cover and be placed in the vacuum drying oven extracting air 8 hours of 25 DEG C, to make calcium chloride load on activated carbon, take out again and leave standstill 24 hours under normal pressure, finally be placed in 1,2-dichloroethanes cracking catalyst E1 (wherein calcium chloride accounts for the 9.8wt% of this overall catalyst weight) of the dry rear obtained embodiment 1 of 120 DEG C of vacuum drying ovens.
Embodiment 2 load cesium chloride
Except the 10wt% calcium chloride water of step (b) is changed into except the 10wt% cesium chloride aqueous solution, 1 of embodiment 2, the method for making of 2-dichloroethanes cracking catalyst is identical with embodiment 1,1,2-dichloroethanes cracking catalyst E2 (wherein cesium chloride accounts for the 9.7wt% of this overall catalyst weight) of obtained embodiment 2.
Embodiment 3 load cesium chloride and potassium chloride
Except the 10wt% calcium chloride water of step (b) is changed into except 9wt% cesium chloride, 1wt% potassium chloride solution, 1 of embodiment 3, the method for making of 2-dichloroethanes cracking catalyst is identical with embodiment 1,1,2-dichloroethanes cracking catalyst E3 (wherein cesium chloride and potassium chloride account for the 9.7wt% of this overall catalyst weight altogether) of obtained embodiment 3.
Comparative example load barium chloride
Except the 10wt% calcium chloride water of step (b) is changed into except 10wt% barium chloride solution, 1 of comparative example, the method for making of 2-dichloroethanes cracking catalyst is identical with embodiment 1,1,2-dichloroethanes cracking catalyst CE (wherein barium chloride accounts for the 9.8wt% of this overall catalyst weight) of obtained comparative example.
Application examples cracking 1,2-dichloroethanes
With constant displacement pump by 1,2-dichloroethanes liquid passes into preheating vaporization (temperature is 200 DEG C) in an evaporimeter, pass into respectively again and be filled with 1 of 85g embodiment 1-3 and comparative example separately, the 2-dichloroethanes cracking fixed bed reactors (1 of catalyst E1-E3 and CE, the purity of 2-dichloroethanes is 99.9%), gas space velocity hourly (GHSV) is set as 550-560h
-1holdup time is 10 seconds, reaction temperature is 250 DEG C (reactor outlet temperature is about 260 DEG C), pass into a condenser respectively again, to carry out 1,2-dichloroethanes and vinyl chloride, being separated of hydrogen chloride, then rectifying separating chlorine ethene and hydrogen chloride, finally carry out following EDC conversion ratio respectively and VCM optionally tests, result is as shown in table 1 below.
Test
EDC conversion ratio (EDCConversion)
VCM selective (VCMSelectivity)
Table 1
| Catalyst | EDC conversion ratio | VCM is selective | |
| Embodiment 1 | Calcium chloride/active carbon | 85.65％ | 99.5％ |
| Embodiment 2 | Cesium chloride/active carbon | 88.85％ | 98.77％ |
| Embodiment 3 | Cesium chloride/potassium chloride/active carbon | 87.84％ | 98.45％ |
| Comparative example | Barium chloride/active carbon | 60.84％ | 95％ |
Can be learnt by upper table 1,1 of embodiment 1-3,2-dichloroethanes cracking catalyst E1-E3 passes through catalysis 1 of the present invention, the method of 2-dichloroethanes cracking, can make EDC conversion ratio reach 85.65-88.85%, and its VCM is selective reaches 98.45-99.5%, show catalyst of the present invention and method can under relatively mild operating condition, make the cracking of 1,2-dichloroethanes generate vinyl chloride and hydrogen chloride, and there is high conversion and high selectivity; And the catalyst CE of comparative example is by method of the present invention, only can obtains lower EDC conversion ratio (60.84%) and VCM selective (95%), comparatively not be suitable for catalytic cracking reaction of the present invention.
In sum, the present invention 1,2-dichloroethanes cracking catalyst and catalysis 1, the method of 2-dichloroethanes cracking can be carried out under compared with the mild operating conditions of low reaction temperatures, and there is high EDC conversion ratio and high VCM selective, effectively can reduce the production cost (low power consuming) of vinyl chloride and promote its productivity effect, therefore really can reach object of the present invention.
The above, be only embodiments of the invention, when not limiting scope of the invention process with this, the simple equivalence namely generally done according to claims of the present invention and patent specification content changes and modifies, and all still remains within the scope of the patent.
Claims (10)
1. a dichloroethanes cracking catalyst, comprises:
One carrier; And
Be carried on the first metal chloride on described carrier,
Wherein, described first metal chloride is selected from calcium chloride, cesium chloride or its combination.
2. 1,2-dichloroethanes cracking catalyst according to claim 1, also comprises the second metal chloride be carried on described carrier, and wherein, this second metal chloride is selected from barium chloride, potassium chloride or its combination.
3. 1,2-dichloroethanes cracking catalyst according to claim 1, wherein, be 100wt% meter with the gross weight of this 1,2-dichloroethanes cracking catalyst, the weight range of described first metal chloride is 9-80wt%.
4. according to claim 11,2-dichloroethanes cracking catalyst, wherein, with this 1, the gross weight of 2-dichloroethanes cracking catalyst is 100wt% meter, and the weight summation scope of described first metal chloride and described second metal chloride is 9-80wt%.
5. 1,2-dichloroethanes cracking catalyst according to claim 1, wherein, described carrier is selected from carbon material, inorganic oxide or its combination.
6. 1,2-dichloroethanes cracking catalyst according to claim 1, wherein, the surface area of described carrier is 100-1000m
2/ g.
7. 1,2-dichloroethanes cracking catalyst according to claim 1, wherein, the average particle size range of described carrier is 0.05-10mm.
8. a catalysis 1, the method of 2-dichloroethanes cracking, comprise make 1,2-dichloroethanes gas with 1, a 2-dichloroethanes cracking catalyst exposure according to claim 1 under carry out cracking reaction, to generate vinyl chloride and hydrogen chloride, wherein, described 1,2-dichloroethanes cracking catalyst is filled in a fixed bed or a thermopnore, and in described cracking reaction, gas space velocity scope hourly is 100-1000h
-1.
9. the method for catalysis 1,2-dichloroethanes according to claim 8 cracking, the temperature range of described cracking reaction is 150-300 DEG C.
10. the method for catalysis 1,2-dichloroethanes according to claim 8 cracking, the holdup time scope of described 1,2-dichloroethanes gas on described 1,2-dichloroethanes cracking catalyst is 5-50 second.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW103136480A TWI498160B (en) | 2014-10-22 | 2014-10-22 | Catalyst and method for cracking 1,2-dichloroethane |
| TW103136480 | 2014-10-22 |
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| Publication Number | Publication Date |
|---|---|
| CN105268457A true CN105268457A (en) | 2016-01-27 |
| CN105268457B CN105268457B (en) | 2017-08-25 |
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| CN201510688115.9A Active CN105268457B (en) | 2014-10-22 | 2015-10-22 | Catalyst for cracking 1, 2-dichloroethane and method for catalyzing 1, 2-dichloroethane cracking |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI610907B (en) * | 2016-08-11 | 2018-01-11 | 臺灣塑膠工業股份有限公司 | Method of producing vinyl chloride |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
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| CN102030608A (en) * | 2010-11-22 | 2011-04-27 | 华东理工大学 | Method for preparing vinylidene chloride by gas-phase catalytic cracking |
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| CN102773086A (en) * | 2012-08-17 | 2012-11-14 | 新疆化工设计研究院 | 1, 2-dichloroethane cracking catalyst, as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3629354A (en) * | 1969-07-14 | 1971-12-21 | Ethyl Corp | Halogenated hydrocarbons |
| DE3007634C2 (en) * | 1980-02-29 | 1982-08-19 | Hans-Jürgen Dipl.-Chem. Dr. 7808 Waldkirch Pettelkau | Process for the production of vinyl chloride |
-
2014
- 2014-10-22 TW TW103136480A patent/TWI498160B/en active
-
2015
- 2015-10-22 CN CN201510688115.9A patent/CN105268457B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009154054A (en) * | 2007-12-25 | 2009-07-16 | Tokuyama Corp | Dehydrohalogenation catalyst |
| CN102140054A (en) * | 2010-01-28 | 2011-08-03 | 中国中化股份有限公司 | Preparation method of tetrafluoromethane |
| CN102030608A (en) * | 2010-11-22 | 2011-04-27 | 华东理工大学 | Method for preparing vinylidene chloride by gas-phase catalytic cracking |
| CN102267863A (en) * | 2011-05-16 | 2011-12-07 | 江苏安迪化学药业有限公司 | Method for preparing trichloroethylene and perchloroethylene from dichloroethane as raw material |
| CN102773086A (en) * | 2012-08-17 | 2012-11-14 | 新疆化工设计研究院 | 1, 2-dichloroethane cracking catalyst, as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI610907B (en) * | 2016-08-11 | 2018-01-11 | 臺灣塑膠工業股份有限公司 | Method of producing vinyl chloride |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201615273A (en) | 2016-05-01 |
| CN105268457B (en) | 2017-08-25 |
| TWI498160B (en) | 2015-09-01 |
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